An artificial [FeFe]-hydrogenase mimic with organic chromophore-linked thiolate bridges for the photochemical production of hydrogen

An artificial FeFe]-hydrogenase (FeFe]-H₂ase) mimic 3II, consisting of dual organic chromophores covalently assembled to the Fe₂S₂] active site, was constructed for light-driven hydrogen evolution. The structural conformation of synthetic photocatalyst was characterized crystallographically and spectroscopically. The photo-induced intramolecular electron transfer was evidently demonstrated by the combination of electrochemical, steady-state, and transient absorption spectroscopic studies. Finally, a remarkable activity was obtained in the present photocatalytic system, indicating the covalent incorporation of photosensitizer and catalytic center as a promising strategy to construct inexpensive, easily accessible FeFe]-H₂ase model photocatalysts.